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Elektronendichte-Verteilungen in Metallorganischen Verbindungen. Wechselnde Struktur- und Bindungsverhältnisse in dimeren metallorganischen Nickel-Hydriden mit Ionenpaar-Beziehungen zu den Hauptgrupppen-Metallen Natrium und Lithium

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Goddard,  Richard
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Krüger,  Carl
Service Department Krüger (XRAY), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Pörschke,  Klaus-Richard
Research Group Pörschke, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Wilke,  Günther
Research Department Wilke, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Goddard, R., Krüger, C., Pörschke, K.-R., & Wilke, G. (1986). Elektronendichte-Verteilungen in Metallorganischen Verbindungen. Wechselnde Struktur- und Bindungsverhältnisse in dimeren metallorganischen Nickel-Hydriden mit Ionenpaar-Beziehungen zu den Hauptgrupppen-Metallen Natrium und Lithium. Journal of Organometallic Chemistry, 308(1), 85-103. doi: 10.1016/S0022-328X(00)99524-X.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-BF3C-E
Abstract
The compounds [[(C2H4)2Ni]2H][Na(TMEDA)2] (I) and [[(C2H4)2Ni]2H]-[Li(CH3)2NCH2CH2N(CH3)CH2CH2N(CH3)2] (II) have been investigated by high resolution X-ray techniques. Compound I is found to exist as distinct ions which are well-separated in the unit cell, while II shows an ion pair contact between the lithium ion part and one nickel atom, one ethene group, and the hydride in the anion. This latter interaction has little effect on the geometry of the anion, which is similar in both compounds. Each nickel atom is surrounded by a trigonal-planar coordination geometry comprising two ethene groups and the bridging hydrige. The Ni-H-Ni bridge is non-linear and the angle at the hydrogen atom is 131 and 111°, respectively. The unusual geometry adopted by the anion is explained in terms of an interaction between the two nickel atoms involving the empty p-orbital on one metal with the filled d-orbitals on the other. The bonding situation obtained from semi-empirical molecular orbital calculations is in accord with the observed electron density distributions.